Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
9
5
2009
10.5194/acpd-9-21669-2009
http://www.atmos-chem-phys-discuss.net/9/21669/2009/
http://www.atmos-chem-phys-discuss.net/9/21669/2009/acpd-9-21669-2009.html
http://www.atmos-chem-phys-discuss.net/9/21669/2009/acpd-9-21669-2009.pdf
21669
21716
2009-10-15
Molecular characterization of urban organic aerosol in tropical India: contributions of biomass/biofuel burning, plastic burning, and fossil fuel combustion
P. Q. Fu
K. Kawamura
kawamura@lowtem.hokudai.ac.jp
C. M. Pavuluri
T. Swaminathan
Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, Japan
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600036, India
Organic molecular composition of PM<sub>10</sub> samples, collected at Chennai in tropical
India, was studied using capillary gas chromatography/mass spectrometry. Twelve organic
compound classes were detected in the aerosols, including aliphatic lipids, sugar compounds,
lignin products, terpenoid biomarkers, sterols, aromatic acids, phthalates, hopanes, and polycyclic aromatic hydrocarbons (PAHs). At daytime, phthalates was found to be the most abundant
compound class; while at nighttime, fatty acids was the dominant one. Concentrations of
total quantified organics were higher in summer (611–3268 ng m<sup>−3</sup>, average
1586 ng m<sup>−3</sup>) than in winter (362–2381 ng m<sup>−3</sup>,
1136 ng m<sup>−3</sup>), accounting for 11.5±1.93% and 9.35±1.77% of
organic carbon mass in summer and winter, respectively. Di-(2-ethylhexyl) phthalate,
C<sub>16</sub> fatty acid, and levoglucosan were identified as the most abundant single
compounds. The nighttime maxima of most organics in the aerosols indicate a land/sea breeze
effect in tropical India, although some other factors such as local emissions and long-range
transport may also influence the composition of organic aerosols. The abundances of anhydrosugars
(e.g., levoglucosan), lignin and resin products, hopanes and PAHs in the Chennai aerosols suggest that biomass burning and
fossil fuel combustion are significant sources of organic aerosols in tropical India. Interestingly,
terephthalic acid was maximized at nighttime, which is different from those of phthalic and
isophthalic acids. A positive correlation was found between the concentration of 1,3,5-triphenylbenzene (a tracer
for plastic burning) and terephthalic acid, suggesting that field burning of municipal
solid wastes including plastics is a significant source of terephthalic acid. This study
demonstrates that, in addition to biomass burning and fossil fuel combustion, the
open-burning of plastics also contributes to the organic aerosols in South Asia.
Andreae,~M O. and Rosenfeld,~D.: Aerosol-cloud-precipitation interactions. Part 1. The nature and sources of cloud-active aerosols, Earth-Sci. Rev., 89, 13–41, 2008.
Bauer,~H., Claeys,~M., Vermeylen,~R., Schueller,~E., Weinke,~G., Berger,~A., and Puxbaum,~H.: Arabitol and mannitol as tracers for the quantification of airborne fungal spores, Atmos. Environ., 42, 588–593, 2008.
Bieleski,~R L.: Onset of phloem export from senescent petals of daylily, Plant Physiol., 109, 557–565, 1995.
bin Abas,~M R., Simoneit,~B R T., Elias,~V., Cabral,~J A., and Cardoso,~J N.: Composition of higher molecular weight organic matter in smoke aerosol from biomass combustion in Amazonia, Chemosphere, 30, 995–1015, 1995.
Chowdhury,~Z., Zheng,~M., Schauer,~J J., Sheesley,~R J., Salmon,~L., Cass,~G R., and Russell,~A.: Speciation of ambient fine organic carbon particles and source apportionment of \chemPM_2.5 in Indian cities,~J. Geophys. Res. Atmos., 112, D15303, doi:10.1029/2007JD008386, 2007.
Crutzen,~P J. and Andreae,~M O.: Biomass burning in the tropics: Impact on atmospheric chemistry and biogeochemical cycles, Science, 250, 1669–1678, 1990.
Forstner,~H J L., Flagan,~R C., and Seinfeld,~J H.: Secondary organic aerosol from the photooxidation of aromatic hydrocarbons: Molecular composition, Environ. Sci. Technol., 31, 1345–1358, 1997.
Fraser,~M P., Cass,~G R., and Simoneit,~B R T.: Air quality model evaluation data for organics. 6. \chemC_3–\chemC_24 organic acids, Environ. Sci. Technol., 37, 446–453, 2003.
Fu,~P., Kawamura,~K., Okuzawa,~K., Aggarwal,~S G., Wang,~G., Kanaya,~Y., and Wang,~Z.: Organic molecular compositions and temporal variations of summertime mountain aerosols over Mt. Tai, North China Plain,~J. Geophys. Res. Atmos., 113, D19107, doi:10.1029/2008JD009900, 2008.
Fu,~P., Kawamura,~K., and Barrie,~L A.: Photochemical and other sources of organic compounds in the Canadian high Arctic aerosol pollution during winter-spring, Environ. Sci. Technol., 43, 286–292, 2009a.
Fu,~P., Kawamura,~K., Pavuluri,~C M., Chen,~J., and Swaminathan,~T.: Molecular characterization of urban organic aerosol in tropical India: Contribution of biogenic photooxidation and source apportionment, in preparation, 2009b.
Gagosian,~R B., Zafiriou,~O C., Peltzer,~E T., and Alford,~J B.: Lipid in aerosols from the tropical North Pacific: Temporal variability,~J. Geophys. Res., 87, 11133–11144, 1982.
Graber,~E R. and Rudich,~Y.: Atmospheric HULIS: How humic-like are they? A~comprehensive and critical review, Atmos. Chem. Phys., 6, 729–753, 2006.
Graham,~B., Guyon,~P., Taylor,~P E., Artaxo,~P., Maenhaut,~W., Glovsky,~M M., Flagan,~R C., and Andreae,~M O.: Organic compounds present in the natural Amazonian aerosol: Characterization by gas chromatography-mass spectrometry,~J. Geophys. Res. Atmos., 108(D24), 4766, doi:4710.1029/2003JD003990, 2003.
Gustafsson, Ö., Kruså,~M., Zencak,~Z., Sheesley,~R J., Granat,~L., Engström,~E., Praveen,~P S., Rao,~P S P., Leck,~C., and Rodhe,~H.: Brown clouds over South Asia: Biomass or fossil fuel combustion?, Science, 323, 495–498, 2009.
Hopke,~P K.: Receptor Modeling in Environmental Chemistry, John Wiley and Sons, New York, 1985.
Kanakidou,~M., Seinfeld,~J H., Pandis,~S N., Barnes,~I., Dentener,~F J., Facchini,~M C., Van Dingenen,~R., Ervens,~B., Nenes,~A., Nielsen,~C J., Swietlicki,~E., Putaud,~J P., Balkanski,~Y., Fuzzi,~S., Horth,~J., Moortgat,~G K., Winterhalter,~R., Myhre,~C E L., Tsigaridis,~K., Vignati,~E., Stephanou,~E G., and Wilson,~J.: Organic aerosol and global climate modelling: a~review, Atmos. Chem. Phys., 5, 1053–1123, 2005.
Kawamura,~K. and Gagosian,~R B.: Implications of $\omega $-oxocarboxylic acids in the remote marine atmosphere for photo-oxidation of unsaturated fatty acids, Nature, 325, 330–332, 1987.
Kawamura,~K. and Kaplan,~I R.: Motor exhaust emissions as a~primary source for dicarboxylic acids in Los Angels ambient air, Environm. Sci. Technol., 21, 105–110, 1987.
Kawamura,~K., Kosaka,~M., and Sempéré,~R.: Distributions and seasonal changes of hydrocarbons in urban aerosols and rainwaters, \textitChikyukagaku (Geochemistry), 29, 1–15, 1995.
Kawamura,~K. and Sakaguchi,~F.: Molecular distributions of water soluble dicarboxylic acids in marine aerosols over the Pacific Ocean including tropics,~J. Geophys. Res. Atmos., 104(D3), 3501–3509, 1999.
Kawamura,~K., Steinberg,~S., and Kaplan,~I R.: Homologous series of \chemC_1–\chemC_10 monocarboxylic acids and \chemC_1–\chemC_6 carbonyls in Los Angeles air and motor vehicle exhausts, Atmos. Environ., 34, 4175–4191, 2000.
Kawamura,~K., Ishimura,~Y., and Yamazaki,~K.: Four years' observations of terrestrial lipid class compounds in marine aerosols from the western North Pacific, Global Biogeochem. Cy., 17, 1003, doi:1010.1029/2001GB001810, 2003.
Lelieveld,~J., Crutzen,~P J., Ramanathan,~V., Andreae,~M O., Brenninkmeijer,~C A M., Campos,~T., Cass,~G R., Dickerson,~R R., Fischer,~H., de Gouw,~J A., Hansel,~A., Jefferson,~A., Kley,~D., de Laat,~A T J., Lal,~S., Lawrence,~M G., Lobert,~J M., Mayol-Bracero,~O L., Mitra,~A P., Novakov,~T., Oltmans,~S J., Prather,~K A., Reiner,~T., Rodhe,~H., Scheeren,~H A., Sikka,~D., and Williams,~J.: The Indian Ocean Experiment: Widespread air pollution from South and Southeast Asia, Science, 291, 1031–1036, 2001.
Medeiros,~P M., Conte,~M H., Weber,~J C., and Simoneit,~B R T.: Sugars as source indicators of biogenic organic carbon in aerosols collected above the Howland Experimental Forest, Maine, Atmos. Environ., 40, 1694–1705, 2006.
Medeiros,~P M. and Simoneit,~B R T.: Source profiles of organic compounds emitted upon combustion of green vegetation from temperate climate forests, Environ. Sci. Technol., 42, 8310–8316, 2008.
Mochida,~M., Kitamori,~Y., Kawamura,~K., Nojiri,~Y., and Suzuki,~K.: Fatty acids in the marine atmosphere: Factors governing their concentrations and evaluation of organic films on sea-salt particles,~J. Geophys. Res. Atmos., 107(D17), 4325, doi:4310.1029/2001JD001278, 2002.
Mochida,~M., Kawabata,~A., Kawamura,~K., Hatsushika,~H., and Yamazaki,~K.: Seasonal variation and origins of dicarboxylic acids in the marine atmosphere over the western North Pacific,~J. Geophys. Res. Atmos., 108(D6), 4193, doi:4110.1029/2002JD002355, 2003.
Nolte,~C G., Schauer,~J J., Cass,~G R., and Simoneit,~B R T.: Highly polar organic compounds present in wood smoke and in the ambient atmosphere, Environ. Sci. Technol., 35, 1912–1919, 2001.
Oros,~D R. and Simoneit,~B R T.: Identification and emission factors of molecular tracers in organic aerosols from biomass burning Part 1. Temperate climate conifers, Appl. Geochem., 16, 1513–1544, 2001a.
Oros,~D R. and Simoneit,~B R T.: Identification and emission factors of molecular tracers in organic aerosols from biomass burning Part 2. Decidous trees, Appl. Geochem., 16, 1545–1565, 2001b.
Pöschl,~U.: Atmospheric aerosols: Composition, transformation, climate and health effects, Angew. Chem. Int. Ed., 44, 7520–7540, 2005.
Pavuluri,~C M., Kawamura,~K., and Swaminathan,~T.: Water-soluble organic carbon, dicarboxylic acids, ketoacids and $\alpha $-dicarbonyl in tropical Indian aerosols,~J. Geophys. Res. Atmos., revised, 2009a.
Pavuluri,~P C., Kawamura,~K., Aggarwal,~S G., Tachibana,~E., and Swaminathan,~T.: Carbonaceous and inorganic ion components and stable carbon isotopic composition of total carbon in tropical Indian aerosols from a~coastal mega-city Chennai: Implications for local emissions and long-range atmospheric transport, in preparation, 2009b.
Ramanathan,~V., Chung,~C., Kim,~D., Bettge,~T., Buja,~L., Kiehl,~J T., Washington,~W M., Fu,~Q., Sikka,~D R., and Wild,~M.: Atmospheric brown clouds: Impacts on South Asia climate and hydrological cycle, PNAS, 102, 5326–5333, 2005.
Robinson,~A L., Donahue,~N M., and Rogge,~W F.: Photochemical oxidation and changes in molecular composition of organic aerosol in the regional context,~J. Geophys. Res. Atmos., 111, D03302, doi:10.1029/2005JD006265, 2006.
Robinson,~A L., Donahue,~N M., Shrivastava,~M K., Weitkamp,~E A., Sage,~A M., Grieshop,~A P., Lane,~T E., Pierce,~J R., and Pandis,~S N.: Rethinking organic aerosols: Semivolatile emissions and photochemical aging, Science, 315, 1259–1262, 2007.
Rogge,~W F., Hildemann,~L M., Mazurek,~M A., Cass,~G R., and Simoneit,~B R T.: Source of fine organic aerosols: 1. Charbroilers and meat cooking operations, Environ. Sci. Technol., 25, 1112–1125, 1991.
Rogge,~W F., Hildemann,~L M., Mazurek,~M A., Cass,~G R., and Simoneit,~B R T.: Sources of fine organic aerosol: 2. Noncatalyst and catalyst-equipped automobiles and heavy-duty diesel trucks, Environ. Sci. Technol., 27, 636–651, 1993.
Rogge,~W F., Hildemann,~L M., Mazurek,~M A., Cass,~G R., and Simoneit,~B R T.: Mathematical modeling of atmospheric fine particle-associated primary organic compound concentrations,~J. Geophys. Res. Atmos., 101(D14), 19379–19394, 1996.
Rudich,~Y., Donahue,~N M., and Mentel,~T F.: Aging of organic aerosol: Bridging the gap between laboratory and field studies, Ann. Rev. Phys. Chem., 58, 321–352, 2007.
Schauer,~J J., Kleeman,~M J., Cass,~G R., and Simoneit,~B R T.: Measurement of emissions from air pollution sources. 2. \chemC_1 through \chemC_30 organic compounds from medium duty diesel trucks, Environ. Sci. Technol., 33, 1578–1587, 1999.
Schauer,~J J., Kleeman,~M J., Cass,~G R., and Simoneit,~B R T.: Measurement of emissions from air pollution sources. 3. \chemC_1–\chemC_29 organic compounds from fireplace combustion of wood, Environ. Sci. Technol., 35, 1716–1728, 2001.
Schauer,~J J., Kleeman,~M J., Cass,~G R., and Simoneit,~B R T.: Measurement of emissions from air pollution sources. 5. \chemC_1–\chemC_32 organic compounds from gasoline-powered motor vehicles, Environ. Sci. Technol., 36, 1169–1180, 2002.
Seinfeld,~J H.: Black carbon and brown clouds, Nature Geosci., 1, 15–16, 2008.
Sheesley,~R J., Schauer,~J J., Chowdhury,~Z., Cass,~G R., and Simoneit,~B R T.: Characterization of organic aerosols emitted from the combustion of biomass indigenous to South Asia,~J. Geophys. Res. Atmos., 108(D9), 4285, doi:10.1029/2002JD002981, 2003.
Sidhu,~S., Gullett,~B., Striebich,~R., Klosterman,~J., Contreras,~J., and DeVito,~M.: Endocrine disrupting chemical emissions from combustion sources: diesel particulate emissions and domestic waste open burn emissions, Atmos. Environ., 39, 801–811, 2005.
Simoneit,~B R T., Sheng,~G Y., Chen,~X J., Fu,~J M., Zhang,~J., and Xu,~Y P.: Molecular marker study of extractable organic-matter in aerosols from urban areas of China, Atmos. Environ. A, 25, 2111–2129, 1991.
Simoneit,~B R T. and Elias,~V O.: Organic tracers from biomass burning in atmospheric particulate matter over the ocean, Mar. Chem., 69, 301–312, 2000.
Simoneit,~B R T.: Biomass burning – a~review of organic tracers for smoke from incomplete combustion, Appl. Geochem., 17, 129–162, 2002.
Simoneit,~B R T., Kobayashi,~M., Mochida,~M., Kawamura,~K., Lee,~M., Lim,~H J., Turpin,~B J., and Komazaki,~Y.: Composition and major sources of organic compounds of aerosol particulate matter sampled during the ACE-Asia campaign,~J. Geophys. Res. Atmos., 109, D19S10, doi:10.1029/2004JD004598, 2004.
Simoneit,~B R T., Medeiros,~P M., and Didyk,~B M.: Combustion products of plastics as indicators for refuse burning in the atmosphere, Environ. Sci. Technol., 39, 6961–6970, 2005.
Stohl, A., Berg, T., Burkhart, J. F., Fj\'æfdraa, A. M., Forster, C., Herber, A., Hov, Ø., Lunder, C., McMillan, W. W., Oltmans, S., Shiobara, M., Simpson, D., Solberg, S., Stebel, K., Ström, J., Tørseth, K., Treffeisen, R., Virkkunen, K., and Yttri, K. E.: Arctic smoke – record high air pollution levels in the European Arctic due to agricultural fires in Eastern Europe in spring 2006, Atmos. Chem. Phys., 7, 511-534, 2007. %Stohl,~A., Berg,~T., Burkhart,~J F.: Arctic smoke-record high air %pollution levels in the European Arctic due to agricultural fires in Eastern Europe in spring 2006, %Atmos. Chem. Phys., 7, 511–534, 2007.\checkCopernicus Publication!
Stone,~E A., Lough,~G C., Schauer,~J J., Praveen,~P S., Corrigan,~C E., and Ramanathan,~V.: Understanding the origin of black carbon in the atmospheric brown cloud over the Indian Ocean,~J. Geophys. Res. Atmos., 122, D22S23, doi:10.1029/2006JD008118, 2007.
Suh,~I., Zhang,~R., Molina,~L T., and Molina,~M J.: Oxidation mechanism of aromatic peroxy and bicyclic radicals from OH-toluene reactions,~J. Am. Chem. Soc., 125, 12655–12665, 2003.
Swan,~S H.: Phthalates may damage male babies, Trac-Trend. Anal. Chem., 24(7), v-v, 2005.
Szidat,~S.: Sources of Asian Haze, Science, 323, 470–471, 2009.
Venkataraman,~C., Habib,~G., Eiguren-Fernandez,~A., Miguel,~A H., and Friedlander,~S K.: Residential biofuels in South Asia: Carbonaceous aerosol emissions and climate impacts, Science, 307, 1454–1456, 2005.
Wan,~E C H. and Yu,~J Z.: Analysis of sugars and sugar polyols in atmospheric aerosols by chloride attachment in liquid chromatography/negative ion electrospray mass spectrometry, Environ. Sci. Technol., 41, 2459–2466, 2007.
Wang,~G., Kawamura,~K., Lee,~S., Ho,~K F., and Cao,~J J.: Molecular, seasonal, and spatial distributions of organic aerosols from fourteen Chinese cities, Environ. Sci. Technol., 40, 4619–4625, 2006a.
Wang,~G., Kawamura,~K., and Lee,~M.: Comparison of organic compositions in dust storm and normal aerosol samples collected at Gosan, Jeju Island, during spring 2005, Atmos. Environ., 43, 219–227, 2009.
Wang,~H B., Kawamura,~K., and Shooter,~D.: Wintertime organic aerosols in Christchurch and Auckland, New Zealand: Contributions of residential wood and coal burning and petroleum utilization, Environ. Sci. Technol., 40, 5257–5262, 2006b.
Wolff,~G T. and Korsog,~P E.: Estimates of the contributions of sources to inhalable particulate concentrations in Detroit, Atmos. Environ., 19, 1399–1409, 1985.
Yassaa,~N., Meklati,~B Y., Cecinato,~A., and Marino,~F.: Organic aerosols in urban and waste landfill of Algiers metropolitan area: Occurence and sources, Environ. Sci. Technol., 35, 306–311, 2001.
Yttri,~K E., Dye,~C., and Kiss,~G.: Ambient aerosol concentrations of sugars and sugar-alcohols at four different sites in Norway, Atmos. Chem. Phys., 7, 4267–4279, 2007.
Zhang,~R Y., Suh,~I., Zhao,~J., Zhang,~D., Fortner,~E C., Tie,~X X., Molina,~L T., and Molina,~M J.: Atmospheric new particle formation enhanced by organic acids, Science, 304, 1487–1490, 2004.
Zheng,~M., Hagler,~G S W., Ke,~L., Bergin,~M H., Wang,~F., Louie,~P K K., Salmon,~L., Sin,~D W M., Yu,~J Z., and Schauer,~J J.: Composition and sources of carbonaceous aerosols at three contrasting sites in Hong Kong,~J. Geophys. Res. Atmos., 111, D20313, doi:10.1029/2006JD007074, 2006.